EP0097892B1 - Verfahren zum hydrothermalen Aufschluss von einen hohen Gehalt an geglühten Aluminiumoxiden aufweisenden chemischen Abfällen und Rückständen - Google Patents

Verfahren zum hydrothermalen Aufschluss von einen hohen Gehalt an geglühten Aluminiumoxiden aufweisenden chemischen Abfällen und Rückständen Download PDF

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Publication number
EP0097892B1
EP0097892B1 EP83105951A EP83105951A EP0097892B1 EP 0097892 B1 EP0097892 B1 EP 0097892B1 EP 83105951 A EP83105951 A EP 83105951A EP 83105951 A EP83105951 A EP 83105951A EP 0097892 B1 EP0097892 B1 EP 0097892B1
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EP
European Patent Office
Prior art keywords
reaction
oxide component
temperatures
residues
aluminium oxide
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Expired
Application number
EP83105951A
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German (de)
English (en)
French (fr)
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EP0097892A1 (de
Inventor
Peter Dr. Christophliemk
Jürgen Dr. von Laufenberg
Rudolf Dr. Novotny
Siegfried Staller
Friedrich-Wilhelm Dr. Diekötter
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to AT83105951T priority Critical patent/ATE40095T1/de
Publication of EP0097892A1 publication Critical patent/EP0097892A1/de
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
    • C01F7/06—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process
    • C01F7/0693—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom by treating aluminous minerals or waste-like raw materials with alkali hydroxide, e.g. leaching of bauxite according to the Bayer process from waste-like raw materials, e.g. fly ash or Bayer calcination dust

Definitions

  • the present invention relates to the recycling of special chemical wastes and residues, which have a high content of annealed aluminum oxides, by hydrothermal reaction with sodium hydroxide solution at a temperature above 180 ° C. to form sodium aluminate solution and their further use.
  • Annealed aluminum oxides are used in a wide variety of technical applications, for example as drying agents and sorbents, as catalysts or catalyst supports or as filter aids. “Used ” products , ie contaminated products of this type that are exhausted in their sorption or catalyst action or that are no longer usable for other reasons, generally have to be landfilled. Depending on the type of loading or contamination, pretreatment or storage in special landfills may also be necessary is.
  • the object of the present invention is therefore to develop a method for the ecologically and economically sensible recycling of chemical wastes and residues which contain annealed aluminum oxides, in which the disadvantages indicated above are avoided.
  • this task relates to achieving the highest possible space / time yield with the lowest possible energy consumption.
  • the temperatures used in calcining and roasting influence the formation of the aluminum oxide phase remaining in stage c: at temperatures up to and including 675 ° C., ⁇ -Al 2 O 3 results without aluminum oxide being converted into the a phase. Only at 725 ° C. does ⁇ -A ⁇ 2 O 3 result , the formation of which is undesirable in the process described, since the a-phase of Al 2 0 3 does not give the catalyst the required catalytic properties. In this way, up to 88% and 96% of the aluminum oxide, for example, can be converted into a soluble form using a calcining and roasting temperature of 625 ° C. using the method described.
  • the annealed aluminum oxides (including a-Al 2 O 3 ) contained in the above-mentioned residues can be reacted with sodium hydroxide to give soluble products of the sodium aluminate type.
  • the solution containing sodium aluminate in turn, can be used for further chemical reactions, depending on the contamination and the cleaning operation that may be required.
  • reaction time required to largely dissolve the annealed aluminum oxides can be shortened; In the context of a technical implementation, however, reaction temperatures of a maximum of 250 ° C. and alkali concentrations of a maximum of 50% NaOH in the contact solution should advantageously not be exceeded.
  • the aluminum oxide-containing solid should be introduced as finely as possible for a rapid reaction.
  • the reaction mixture is kept in motion at least to such an extent that the finely suspended solid does not sediment.
  • the aluminate liquor formed is filtered if there are noticeable amounts of residue, depending on the intended further use of the aluminate liquor.
  • reaction vessels or reactors customary for hydrothermal high-pressure syntheses such as, for example, rotating or static vessels and tubular reactors.
  • aluminum oxide component is understood to mean the chemical wastes and residues which have a high content of annealed aluminum oxides, preferably of the type a-A1 2 0 3 .
  • the hydrothermal conversion is carried out in a rotating, cylindrical pressure vessel which is rotatably mounted about its horizontal axis.
  • the aluminum oxide component and sodium hydroxide solution are introduced into the reaction container in batches.
  • the aqueous solid / sodium hydroxide suspension is then heated to the desired reaction temperature in the rotating pressure vessel.
  • This heating of the reaction mixture can be carried out either indirectly - for example by means of suitable heating elements in the reaction vessel or jacket heating thereof - or directly by introducing water vapor into the reaction vessel - as also shown in the flow diagram as an example.
  • Saturated water vapor is preferably fed to the reaction mixture until the desired reaction temperature is reached because of the increased heating rate, the pressure of the saturated water vapor in the reaction vessel corresponding to this temperature being established at the same time.
  • the table below shows an example of some comparative values between temperature and pressure of saturated water vapor:
  • a static container is used for the hydrothermal reaction.
  • the liquid phase of the reaction mixture at temperatures in the range from 180 to 250 ° C and the pressures of saturated water vapor corresponding to these temperatures is circulated as long as it is circulated through a solid bed containing annealed aluminum oxide in the static reaction vessel with formation of a fluidized bed and through an outside of the Pumped bypass line pumped until the AIP3 concentration in the liquid phase has reached the desired value.
  • the liquid phase is drawn off from the reaction vessel in the upper part and reintroduced into this by a bypass line 5 arranged outside the vessel and an appropriate pump 6 at the lower end of the vessel, so that this liquid flow is always under pressure from below into the solid bed. or into the already formed fluidized bed.
  • liquid phase of the reaction mixture essentially means both the aqueous sodium hydroxide solution used and the sodium aluminate solution formed in the course of the reaction, but which may also contain portions of the whirled alumina component.
  • the reaction mixture is expediently heated to the required reaction temperature by direct introduction of saturated water vapor into the reaction vessel, the water vapor also advantageously being introduced into the bottom end of the vessel (at feed 7 according to FIG. 2) in this way to support whirling up of the solid bed in the sense of forming the fluidized bed essential to the invention.
  • the reaction mixture can additionally be heated indirectly by means of suitable heating elements in the reaction vessel or by jacket heating thereof.
  • the bypass line 5 can, if desired, be equipped with a corresponding heating jacket.
  • saturated water vapor is preferably fed to the reaction mixture until the desired reaction temperature is reached, the pressure of the saturated water vapor in the reaction vessel corresponding to this temperature being established at the same time.
  • reaction mixture After reaching the desired reaction temperature, the reaction mixture is left in the static pressure vessel under constant pumping around the liquid phase under the set temperature / pressure conditions until a sample of the sodium aluminate solution formed reaches the desired Al z 0 3 concentration displays.
  • the reaction times required for this can also be determined empirically in this embodiment in general in the course of a few reaction processes.
  • the sodium aluminate solution which is formed - still under pressure or relaxed to normal pressure - is transferred through lines 8 or 9 to a filter 10.
  • This second preferred embodiment is also suitable for a continuous procedure.
  • the sodium aluminate solution formed is continuously carried out from the reaction vessel and the reaction component is also continuously metered into the same.
  • the introduction of aluminum oxide component and sodium hydroxide solution into the static reaction vessel is expediently carried out using appropriate pressure pumps; the aluminate component is preferably introduced directly into the lower part of the same through an immersion tube arranged in the container. Adherence to the desired reaction temperature and the pressure is ensured by a correspondingly controlled - optionally continuous - supply of saturated water vapor.
  • the sodium aluminate solution obtained is continuously withdrawn from the reaction container and opened, preferably via line 9 transferred the filter.
  • a solid filter is used to separate off the sodium aluminate solution obtained by the process of the invention by filtration.
  • the excess aluminum oxide component already used for the reaction is preferably used as the filter medium for this solid filter from the end hydrothermal synthesis, optionally in a mixture with excess aluminum oxide component from one of the preceding batch-wise reactions or “fresh”, that is to say aluminum oxide component which has not yet been treated hydrothermally.
  • fresh excess aluminum oxide component from one of the preceding batch-wise reactions or “fresh”
  • the excess solid that settles in the lower part of the reaction vessel is first transferred to the filter bed. Any aluminum oxide component still remaining in the reaction vessel can be left in the subsequent reaction or used to prepare the solid filter for one of the subsequent batches.
  • the solid bed of the filter is advantageously processed by a small amount of liquid flowing in from the bottom, which is circulated, for example water or, if appropriate, sodium aluminate solution, in such a way that the fine fractions of the adjusted aluminum component the surface of the filter bed is washed away and thus form a sufficiently effective filter layer.
  • Aluminum hydroxide for example, can be precipitated from the aluminate liquor obtained in the process of the invention in different ways. However, because of the high alkali content of the aluminate solution, their direct use is more economical, e.g. as an aluminate component for the production of aluminum silicates, in particular and preferably of zeolitic sodium aluminum silicate of the NaA type.
  • such masses containing annealed aluminum oxides are preferred which also contain other aluminum-containing components and / or alkali carriers, since the latter are then used in their entirety without pretreatment.
  • filter aids based on aluminum oxide used for the filtration of aluminate lyes are such particularly suitable compositions since they still contain considerable residual amounts of sodium aluminate, aluminum hydroxides and sodium hydroxide solution in addition to the annealed aluminum oxides.
  • Such “used” filter aids would otherwise have to be treated and deposited in a complex manner, but bring additional value in the hydrothermal reaction according to the invention.
  • a filter aid based on ⁇ -Al 2 O 3 used for the filtration of aluminate solutions was used as the aluminum oxide component to be used according to the invention.
  • This "used" moist filter aid still contained considerable amounts of adhering aluminate.
  • the solids content (determined by annealing at 800 ° C. for 1 hour) was 75.5%;
  • the Na 2 O content was determined to be 7.5% and the total Al 2 O 3 content to 68% by X-ray fluoride license analysis. From this total amount of Al 2 0 3 , the proportion of ⁇ -Al 2 O 3 to about 62%, the proportion of Al 2 0 3 from other components (such as sodium metal aluminate and / or aluminum hydroxide) to about 6% could be determined analytically.
  • the suspended solid had a proportion of particles ⁇ 10 ⁇ m in excess of 90%.
  • the heating was carried out by direct introduction of saturated water vapor into the pressure vessel.
  • the speed of the rotating reactor was 6 revolutions per minute.
  • the sodium aluminate solution formed after the indicated reaction time was filtered through a solid filter using the unreacted alumina component.
  • the solution thus obtained contained 13.4% Al 2 0 3 .
  • the sodium aluminate solution formed after the indicated reaction time was filtered through a solid filter using the unreacted aluminate oxide component.
  • the solution thus obtained contained 14.1% Al 2 0 3 .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Processing Of Solid Wastes (AREA)
EP83105951A 1982-06-28 1983-06-18 Verfahren zum hydrothermalen Aufschluss von einen hohen Gehalt an geglühten Aluminiumoxiden aufweisenden chemischen Abfällen und Rückständen Expired EP0097892B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83105951T ATE40095T1 (de) 1982-06-28 1983-06-18 Verfahren zum hydrothermalen aufschluss von einen hohen gehalt an gegluehten aluminiumoxiden aufweisenden chemischen abfaellen und rueckstaenden.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19823224040 DE3224040A1 (de) 1982-06-28 1982-06-28 Verfahren zum hydrothermalen aufschluss von einen hohen gehalt an gegluehten aluminiumoxiden aufweisenden chemischen abfaellen und rueckstaenden
DE3224040 1982-06-28

Publications (2)

Publication Number Publication Date
EP0097892A1 EP0097892A1 (de) 1984-01-11
EP0097892B1 true EP0097892B1 (de) 1989-01-18

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Family Applications (1)

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EP83105951A Expired EP0097892B1 (de) 1982-06-28 1983-06-18 Verfahren zum hydrothermalen Aufschluss von einen hohen Gehalt an geglühten Aluminiumoxiden aufweisenden chemischen Abfällen und Rückständen

Country Status (6)

Country Link
US (1) US4557907A (enrdf_load_stackoverflow)
EP (1) EP0097892B1 (enrdf_load_stackoverflow)
JP (1) JPS5921520A (enrdf_load_stackoverflow)
AT (1) ATE40095T1 (enrdf_load_stackoverflow)
BR (1) BR8303411A (enrdf_load_stackoverflow)
DE (2) DE3224040A1 (enrdf_load_stackoverflow)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5052694A (en) * 1986-07-08 1991-10-01 Eg&G Sealol, Inc. Hydrostatic face seal and bearing
AU6970391A (en) * 1989-12-27 1991-07-24 Alcan International Limited Process for converting dross residues to useful products
AT398750B (de) * 1992-06-17 1995-01-25 Waagner Biro Ag Verfahren zur aluminiumherstellung nach dem bayer-verfahren
AT409350B (de) * 2000-06-28 2002-07-25 Kostjak Michael Dipl Ing Dr Te Verfahren zum herauslösen von metallischem aluminium aus aluminiumhaltigen, festen abfällen

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE711017C (de) * 1936-10-23 1941-09-25 Ture Robert Haglund Verfahren zum Aufschluss tonerdehaltiger Mineralien
US2946658A (en) * 1957-06-26 1960-07-26 Kaiser Aluminium Chem Corp Chemical process for extracting monohydrate alumina containing materials
NL131570C (enrdf_load_stackoverflow) * 1963-07-29
FR1498542A (fr) * 1966-08-18 1967-10-20 Electro Chimie Soc D Perfectionnements à l'épuration des solutions d'aluminate de sodium
US3773890A (en) * 1972-04-14 1973-11-20 Union Carbide Corp Process for extracting values from spent hydrodesulfurization catalysts
US3814701A (en) * 1972-08-09 1974-06-04 Fmc Corp Regeneration of spent alumina
US3859413A (en) * 1972-08-09 1975-01-07 Oil Shale Corp Alumina recovery from oil shale residue
US4113832A (en) * 1977-11-28 1978-09-12 Kaiser Aluminum & Chemical Corporation Process for the utilization of waste materials from electrolytic aluminum reduction systems
US4167316A (en) * 1978-06-26 1979-09-11 Polaroid Corporation Sonar controlled lens focus apparatus

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Gmelins Handbuch der anorganischen Chemie, Band "Aluminium" Teil B (1934), Seite 97 *
Römpps Chemie-Lexikon Band 1 (1972) Seite 138 *

Also Published As

Publication number Publication date
ATE40095T1 (de) 1989-02-15
DE3224040A1 (de) 1983-12-29
DE3378976D1 (en) 1989-02-23
JPH04928B2 (enrdf_load_stackoverflow) 1992-01-09
JPS5921520A (ja) 1984-02-03
EP0097892A1 (de) 1984-01-11
BR8303411A (pt) 1984-02-07
US4557907A (en) 1985-12-10

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